We developed a novel approach for the preparation of N-doped TiO2 photocatalysts by calcining ammonium titanium oxalate at different temperatures. The structures of N-TiO2 were characterized by powder X-ray diffraction, infrared spectroscopy, thermogravimetric analysis, N2 adsorption-desorption isotherms, X-ray photoelectron spectroscopy, diffuse reflectance UV-Vis spectroscopy, and scanning electron microscope. The N-doped TiO2 photocatalysts calcined below 700 ℃ are the pure anatase phase but that calcined at 700 ℃ is a mixture of anatase and rutile phases. The doped N locates at the interstitial site of TiO2 which leads to the narrowing of bad gap of pure anatase N-TiO2. Among all photocatalysts, N-TiO2 photocatalysts calcined at 600 and 400 ℃ exhibit the best performance in the photodegradation of methyl orange under the UV light and all-wavelength light illuminations, respectively; however, because of the perfect crystallinity and the existence of anatase-rutile phase junctions, N-TiO2 photocatalyst calcined at 700 ℃ exhibits the highest specific photodegradation rate, i.e., the highest quantum yield, under both the UV light and all-wavelength light illuminations.